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US4622353A - Epoxy resin-diammonium salt emulsion and process for its production - Google Patents

Epoxy resin-diammonium salt emulsion and process for its production Download PDF

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Publication number
US4622353A
US4622353A US06/681,474 US68147484A US4622353A US 4622353 A US4622353 A US 4622353A US 68147484 A US68147484 A US 68147484A US 4622353 A US4622353 A US 4622353A
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Prior art keywords
epoxy resin
diammonium salt
salt emulsion
emulsion according
acid
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US06/681,474
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Jorn-Volker Weiss
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Huels AG
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Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/281—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5093—Complexes of amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • Epoxy resin-cement mortars chemically compatible with steel and concrete, are especially well suited for this purpose.
  • a plastic-containing binder is disclosed, for example, in DAS No. 1,198,267, consisting of a hydraulic cement, water, an epoxy resin curable at normal temperature, and a curing agent. Preparation of this binder is cumbersome since two premixes must be produced separately from each other and may be combined only immediately prior to use. The relatively brief processing time of about 1-2 hours is the basic drawback not only in using this system but also in all so-called 2K systems (see, for example, DOS No. 2,840,874). After each use, all processing equipment which has been in contact with the binder, must be thoroughly cleaned to avoid clogging and the formation of difficult to remove deposits.
  • U.S. Pat. No. 3,926,886 relates to a 1K epoxy resin-diammonium acetate or formate emulsion consisting of a liquid epoxy resin, water and a substituted diammonium salt, with curing taking place in the presence of cement.
  • the diammonium salt performs a dual function: after reaction with the alkaline-acting cement, the less basic diamine is liberated (a) curing the epoxy resin and (b) serving as an emulsifier.
  • the resultant emulsion may not be stable, especially if the work is to be conducted under extreme weather conditions. Accordingly, the patentees propose to add up to 15% of a commercial emulsifier to the mixture being emulsified. Even so, stability of the emulsion is not certain.
  • EP-Al-00 43 463 acid is added to keep the amine component from reacting with the epoxy resins at elevated temperature; any adducts formed are rendered water-soluble and dispersible by addition of the acid.
  • the goal is to prepare an emulsion from a diammonium salt and an epoxy resin wherein the curing process is initiated at temperatures of above 0° C. only upon addition of an alkaline-reacting compound.
  • Surface-active compounds such as anionic and cationic compounds.
  • German Pat. No. 2,800,323
  • Poly(ethylene oxide) esters of fatty acids Poly(ethylene oxide) esters of fatty acids.
  • East German Pat. No. 135,915 describes 2K dispersions containing a polysulfide, a polyepoxide, and a polyvinyl alcohol, utilized as coating agents or as cement additives. Building materials containing organically bound sulfur are not in general use since it can accelerate the corrosion of steel.
  • German Patent Application No. P 32 22 531.8 corresponding to U.S. Pat. No. 4,442,245
  • German Patent Application No. P 32 22 531.8 corresponding to U.S. Pat. No. 4,442,245
  • German Patent Application No. P 32 22 531.8 corresponding to U.S. Pat. No. 4,442,245
  • German Patent Application No. P 32 22 531.8 corresponding to U.S. Pat. No. 4,442,245
  • German Patent Application No. P 32 22 531.8 corresponding to U.S. Pat. No. 4,442,245
  • German Patent Application No. P 32 22 528.8 corresponding to U.S. Pat. No. 4,440,882
  • the salt of a polyamine or a polyaminoamide with oxalic acid is utilized as the latent curing agent.
  • a further object of this invention is to make improved available emulsions suitable for various restoration and construction purposes.
  • a latent curing agent comprising the salt from a
  • emulsions within the scope of this application, mean not only the two-phase systems formed by dispersing a liquid phase in another liquid phase, but also those systems wherein a solid phase is dispersed in a liquid phase, as well as all transition stages of these two systems.
  • the epoxy resins are liquid compounds based on 2,2-bis(4-hydroxyphenyl)alkanes and epichlorohydrin or glycidol, commercially available as "Eurepox” by Schering, Berlin. Especially suitable are epoxy resins that can be emulsified in water, such as, for example, "Rutapox” VE 2913 by Bakelite GmbH, Duisburg.
  • the latent curing agent is the diammonium salt of an organic acid.
  • suitable diamines have alkylene and cyclohexylene residues substituted by one to three methyl groups.
  • Preferred examples for Formula I are 2,2,4- and/or 2,4,4,-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine), as well as xylylenediamine.
  • a preferred example for a diamine according to Formula II is 4,4'-diamino-3,3'-diamethyldicyclohexylmethane Mixtures of diamines can also be utilized. The amount of diamine used depends on the nature of the epoxy resin, for example, its epoxy value or the mixture ratio of resin and curing agent indicated by the resin manufacturer.
  • the acid used to form a salt with the diamine can be mono- or dibasic, and can contain hydroxy groups and have up to 12 carbon atoms. It can be saturated or unsaturated, aliphatic, cycloaliphatic, or aromatic. Formic acid, acetic acid, oxalic acid, adipic acid, tartaric acid, and phthalic acid are preferred.
  • the amount of water most favorable for an emulsion is essentially dependent on the type of diamine. In case of diamines having relatively small number of carbon atoms, for example seven, less water is required than in case of diamines with larger number of carbon atoms, for example twelve. By varying the amount of water between 30% and 250%, based on the amount of epoxy resin employed, the optimum quantity can be readily determined by comparative tests.
  • the polyvinyl alcohol component is obtained by the saponification of polyvinyl acetate. It has a degree of hydrolysis of at least 70% and a molecular weight of at least 5,000, especially 10,000-100,000 (see Rompps Chemie-Lexikon, 7th edition).
  • the polyoxazoline has a molecular weight of 10,000-100,000 and is obtained by polymerization of 2-alkyl- ⁇ 2 -oxazolines wherein the alkyl group has 1-5 carbon atoms (see DOS. No. 30 36 119 and Angew. Chemie 78: 913 [1966]).
  • the emulsifier is utilized, based on the quantity of epoxy resin, in amounts of 0.5-40% by weight.
  • Undesirable formation of air pores can occur during mixing of the emulsion with fresh concrete. This phenomenon can be suppressed in a simple way by adding 0.5-5% by weight of a defrother, based on the total weight of the emulsion.
  • defrothers based on silicones or hydrocarbons such as, for example, RD defrother emulsion from Dow Corning, Duesseldorf; the defrother "Nopco” by Munzing Chemie GmbH, Heilbronn; or the "Dehydran” types of Henkel KGaA.
  • auxiliary agents can be added to the emulsions, such as concrete thinners and accelerators (see European Laid-Open Application No. 0 090 434).
  • Concrete thinners based on melamine resins such as, for example, "Melment” (manufacturer: Sued Weg Kalkstickstoff-Werke AG, D-8223 Trostberg) serve for increasing the fluidity of mortar mixtures. Their proportion is 0.1-8%, based on the total weight of the emulsion.
  • Accelerators effect a rapid and complete curing of the epoxy resin.
  • Suitable accelerators are N- and P-containing compounds, conventional in principle, especially tertiary amines of up to 20 carbon atoms and esters of phosphorous acids of up to 25 carbon atoms, such as, for example, N-benzyldimethylamine and triphenylphosphite. They are used in amounts of 2-5%, based on the epoxide.
  • the emulsions are prepared by
  • auxiliary agents such as, for example, concrete thinners and accelerators, and
  • Deviations from this usual preparation method are possible and can be advantageous in certain cases.
  • the sequence of adding the acid and the diamine can be reversed, for example. It is also possible to prepare the diammonium salt separately beforehand and then add same to the mixture.
  • the decisive factor is that the pH value of the mixture must lie below 7, better below 6.5, at the time the epoxide is added under agitation.
  • the pH value should not be below 6, since otherwise the hydraulic binder is deprived of too much alkalinity.
  • the mixture is stirred for another 0.5-1.0 hour. In this way, emulsions are obtained which are stable for months at room temperature. In case of the occurrence of phase separation, the mixtures can be rapidly homogenized again by another agitation step.
  • the emulsions according to invention exhibit the property of being cured only in the presence of alkaline agents, such as inorganic bases, cement, and other alkaline-setting binders.
  • alkaline agents such as inorganic bases, cement, and other alkaline-setting binders.
  • curing is customarily conducted in the presence of cement, also suitable are curing mixtures which contain alkali hydroxides or alkaline earth hydroxides, calcium oxide, or other basic-reacting oxides.
  • Mineral fillers such as sand, finely ground silicon dioxide, and similar fillers, do not interfere with the curing process.
  • the emulsions according to the present invention are usable in an extremely variegated fashion in the construction field, wherein particular emphasis is given to application in the restoration of already existing buildings.
  • the emulsions of the invention are especially suited for use in the dry grouting method (method of dry application with a cement gun) (cf. DOS No. 31 36 737).
  • a cement gun method of dry application with a cement gun
  • the present emulsions fulfill this requirement.
  • the water/cement ratio is 0.35-0.65
  • the ratio of epoxide and diamine to cement is 0.035-0.15.
  • Cured epoxy emulsion mortars have, as compared with conventional mortars, a higher resistance against water penetration, even when the water has chemicals, etc. dissolved therein. For this reason, the emulsions are excellently suited for the manufacture of prefabricated concrete parts, such as, for example, wastewater and sewage pipes.
  • Mastic and adhesive compositions based on hydraulically setting binders which are utilized, for example, in the tile art, advantageously contain the disclosed emulsions in amounts of between 3% and 75%. Adhesive strength and processing time correspond to the values required in this art.
  • the emulsions of the great invention are employed for the production of flooring plaster, especially if the surface is subjected to extraordinary loads.
  • a flat-bottomed flask with mechanical agitator is charged with 104 parts by weight of water, 44 parts by weight of an aqueous 10% polyvinyl alcohol solution ("PVAL" GH-20 of Nippon Synthetic Chemical Industry Co., Ltd.), and 4.5 parts by weight of a silicone-containing defrother (RD defrother of Dow Corning, Duesseldorf).
  • PVAL polyvinyl alcohol solution
  • RD defrother RD defrother of Dow Corning, Duesseldorf
  • the diamines are abbreviated in the tables as follows:
  • Example 2 Analogously to Example 1, an emulsion was prepared without, however, an addition of defrother.
  • test specimen was produced in accordance with the standard DIN 1164 from
  • An adhesive composition was prepared from 100 parts by weight of portland cement 35 F and 58 parts by weight of the emulsion according to Example 18 and was cured into test specimens. After 3 days of storage under moist conditions and 4 days of inside storage, the following strength data were determined:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Colloid Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

An epoxy resin-diammonium salt emulsion is based on a liquid epoxy resin, water, an emulsifier and a latent curing agent, wherein the emulsifier is
(a) a polyvinyl alcohol obtained by saponification of polyvinyl acetate with a degree of hydrolysis of at least 70% and a molecular weight of at least 5,000,
(b) a polyoxazoline having a molecular weight of 10,000-100,000, and/or
(c) a copolymer of N-vinylpyrrolidone with
vinyl esters of mono- or dibasic carboxylic acids of up to 6 carbon atoms,
(meth)acrylic esters of mono- and dihydric alcohols of up to 6 carbon atoms,
maleic, fumaric, crotonic acid and/or
styrene
and wherein the latent curing agent is the salt from a
(a) diamine of the formula
H.sub.2 N--CH.sub.2 --R--NH.sub.2 or H.sub.2 N--R--CH.sub.2 --R--NH.sub.2
wherein R is
an optionally substituted C4-9 -alkylene residue,
an optionally substituted C6-9 -cyclo- alkylene residue, or
a C7-9 -aralkylene residue, with
(b) optionally hydroxy-group-containing, aliphatic, cycloaliphatic, or aromatic mono- or dicarboxylic acids of up to 12 carbon atoms.

Description

CROSS REFERENCE TO RELATED APPLICATION
This application is related to commonly assigned application Ser. No. 681,475, filed Dec. 14, 1984.
BACKGROUND OF THE INVENTION
For the past several years, experts have noticed that the condition of many relatively new buildings has deteriorated markedly. Several causes have been cited:
1. While other buildings were often constructed in a massive mode, for esthetic reasons and to keep costs low less massive structures have been preferred in constructing newer buildings.
2. Not only changing weather conditions (temperature, sunlight, moisture), but also to an increasing extent chemical influences (deicing salt, carbon dioxide, nitrogen oxides, sulfur dioxide) contribute toward a rapid deterioration of conventional building materials. The combination of physical changes and chemical attack results in carbonatization of concrete, in elimination of passivation and formation of metal rust, and in peeling off of a structure's facing.
3. At the same time, physical stresses increase, e.g., bridges carry an increased volume of traffic including heavy freight carrying trucks.
Rarely is the tearing down and complete rebuilding of damaged structure economically justified. Obviously, the better approach is to preserve and restore. There is a need for better procedures, and more particularly better materials making it more feasible to effect restoration. Epoxy resin-cement mortars, chemically compatible with steel and concrete, are especially well suited for this purpose.
A plastic-containing binder is disclosed, for example, in DAS No. 1,198,267, consisting of a hydraulic cement, water, an epoxy resin curable at normal temperature, and a curing agent. Preparation of this binder is cumbersome since two premixes must be produced separately from each other and may be combined only immediately prior to use. The relatively brief processing time of about 1-2 hours is the basic drawback not only in using this system but also in all so-called 2K systems (see, for example, DOS No. 2,840,874). After each use, all processing equipment which has been in contact with the binder, must be thoroughly cleaned to avoid clogging and the formation of difficult to remove deposits.
U.S. Pat. No. 3,926,886 relates to a 1K epoxy resin-diammonium acetate or formate emulsion consisting of a liquid epoxy resin, water and a substituted diammonium salt, with curing taking place in the presence of cement. The diammonium salt performs a dual function: after reaction with the alkaline-acting cement, the less basic diamine is liberated (a) curing the epoxy resin and (b) serving as an emulsifier. However, the resultant emulsion may not be stable, especially if the work is to be conducted under extreme weather conditions. Accordingly, the patentees propose to add up to 15% of a commercial emulsifier to the mixture being emulsified. Even so, stability of the emulsion is not certain.
In EP-Al-00 43 463, acid is added to keep the amine component from reacting with the epoxy resins at elevated temperature; any adducts formed are rendered water-soluble and dispersible by addition of the acid. In the present invention, the goal is to prepare an emulsion from a diammonium salt and an epoxy resin wherein the curing process is initiated at temperatures of above 0° C. only upon addition of an alkaline-reacting compound.
The patent literature describes numerous emulsifiers suitable for use in conjunction with aqueous epoxy resin dispersions:
U.S. Pat. No. 3,879,324:
Surface-active compounds, such as anionic and cationic compounds.
Canadian Pat. No. 879,750:
Mixtures of nonylphenoxypoly(ethoxy)19 ethanol and alkylene oxide extended alkyl phenol polyglycol ethers.
German Pat. No. 2,800,323:
Poly(ethylene oxide) esters of fatty acids.
DAS No. 1,669,772:
Addition products of 25-30 moles of alkylene oxide and abietic acid.
U.S. Pat. No. 3,020,250:
Synthetic compounds, proteins.
DOS No. 1,925,941:
Amine-epoxy resin condensation products.
DAS No. 2,332,165:
Mixtures of abietic acid polyglycol esters, polyglycol ethers of fatty acids and/or polyglycol ethers of p-alkyl phenol and long-chain aliphatic alcohols of 8-18 carbon atoms.
East German Pat. No. 135,915 describes 2K dispersions containing a polysulfide, a polyepoxide, and a polyvinyl alcohol, utilized as coating agents or as cement additives. Building materials containing organically bound sulfur are not in general use since it can accelerate the corrosion of steel.
More recently, formulations were developed superior to those described in U.S. Pat. No. 3,926,886 with regard to availability of the amine component, stability of the emulsion and spectrum of usage. German Patent Application No. P 32 22 531.8, corresponding to U.S. Pat. No. 4,442,245, teaches emulsions consisting of an epoxy resin, a primary aliphatic C12-14 -alcohol and/or its adduct with ethylene oxide groups, water, and the salt of an alkylene diamine and oxalic acid. In German Patent Application No. P 32 22 528.8, corresponding to U.S. Pat. No. 4,440,882, the salt of a polyamine or a polyaminoamide with oxalic acid is utilized as the latent curing agent.
Notwithstanding these improvements, stability of the emulsion remains uncertain. Problems occur, particularly, if the epoxy resin itself is not readily emulsifiable in water. Also, the formation of air pores due to entrained air has an adverse effect when such emulsions are used to produce mortars.
Although it is known that it is possible to improve the flexibility of concretes by means of certain polymer additives (European Laid-Open Application No. 0 055 035), it is likewise known that concretes containing polyvinyl acetate have not proven themselves under practical conditions. This is due to the fact that, under the influence of moisture, the polyvinyl acetate is saponified forming polyvinyl alcohol. At the same time, the technical properties of the concrete are impaired (see DOS No. 31 36 737).
OBJECT OF THE INVENTION
Therefore, it is an object of the present invention to provide improved epoxy resin-diammonium salt emulsions.
A further object of this invention is to make improved available emulsions suitable for various restoration and construction purposes.
Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.
SUMMARY OF THE INVENTION
Emulsions have now been discovered which meet these objectives.
The components of the epoxy resin-diammonium salt emulsions according to the present invention can be characterized in greater detail as follows:
a liquid epoxy resin,
water,
an emulsifier comprising
(a) a polyvinyl alcohol obtained by saponification of polyvinyl acetate with a degree of hydrolysis of at least 70% and a molecular weight of at least 5,000,
(b) a polyoxazoline having a molecular weight of 10,000-100,000, and/or
(c) a copolymer of N-vinylpyrrolidone with
vinyl esters of mono- or dibasic carboxylic acids of up to 6 carbon atoms,
(meth)acrylic esters of mono- and dihydric alcohols of up to 6 carbon atoms,
maleic, fumaric, crotonic acid and/or
styrene, and
a latent curing agent comprising the salt from a
(a) diamine of Formula I or II
H.sub.2 N--CH.sub.2 --R--NH.sub.2                          (I)
H.sub.2 N--R--CH.sub.2 --R--NH.sub.2                       (II)
wherein R is
an optionally substituted C4-9 -alkylene residue,
an optionally substituted C6-9 -cyclo-alkylene residue, or
an optionally substituted C7-9 -aralkylene residue,
with
(b) optionally hydroxy-group-containing, aliphatic, cycloaliphatic, or aromatic mono- or dicarboxylic acids of up to 12 carbon atoms,
It is to be expressly pointed out that emulsions, within the scope of this application, mean not only the two-phase systems formed by dispersing a liquid phase in another liquid phase, but also those systems wherein a solid phase is dispersed in a liquid phase, as well as all transition stages of these two systems.
DETAILED DISCUSSION
The epoxy resins are liquid compounds based on 2,2-bis(4-hydroxyphenyl)alkanes and epichlorohydrin or glycidol, commercially available as "Eurepox" by Schering, Berlin. Especially suitable are epoxy resins that can be emulsified in water, such as, for example, "Rutapox" VE 2913 by Bakelite GmbH, Duisburg.
The latent curing agent is the diammonium salt of an organic acid. Especially suitable diamines have alkylene and cyclohexylene residues substituted by one to three methyl groups. Preferred examples for Formula I are 2,2,4- and/or 2,4,4,-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine), as well as xylylenediamine. A preferred example for a diamine according to Formula II is 4,4'-diamino-3,3'-diamethyldicyclohexylmethane Mixtures of diamines can also be utilized. The amount of diamine used depends on the nature of the epoxy resin, for example, its epoxy value or the mixture ratio of resin and curing agent indicated by the resin manufacturer.
The acid used to form a salt with the diamine can be mono- or dibasic, and can contain hydroxy groups and have up to 12 carbon atoms. It can be saturated or unsaturated, aliphatic, cycloaliphatic, or aromatic. Formic acid, acetic acid, oxalic acid, adipic acid, tartaric acid, and phthalic acid are preferred.
The amount of water most favorable for an emulsion is essentially dependent on the type of diamine. In case of diamines having relatively small number of carbon atoms, for example seven, less water is required than in case of diamines with larger number of carbon atoms, for example twelve. By varying the amount of water between 30% and 250%, based on the amount of epoxy resin employed, the optimum quantity can be readily determined by comparative tests.
With regard to the emulsifier, the polyvinyl alcohol component is obtained by the saponification of polyvinyl acetate. It has a degree of hydrolysis of at least 70% and a molecular weight of at least 5,000, especially 10,000-100,000 (see Rompps Chemie-Lexikon, 7th edition). The polyoxazoline has a molecular weight of 10,000-100,000 and is obtained by polymerization of 2-alkyl-Δ2 -oxazolines wherein the alkyl group has 1-5 carbon atoms (see DOS. No. 30 36 119 and Angew. Chemie 78: 913 [1966]). Copolymers N-vinylpyrrolidone with
(a) vinyl esters of mono- or dibasic carboxylic acids of up to 6 carbon atoms,
(b) (meth)acrylic esters of mono- and dihydric alcohols of up to 6 carbon atoms,
(c) maleic, fumaric, crotonic acid and/or
(d) styrene
are described in the following German Pat. Nos. 2,218,935; 2,255,263; 2,456,807; and 2,514,127. Especially suitable is "Collacral" VL, a product of BASF, Ludwigshafen. The emulsifier is utilized, based on the quantity of epoxy resin, in amounts of 0.5-40% by weight.
Undesirable formation of air pores can occur during mixing of the emulsion with fresh concrete. This phenomenon can be suppressed in a simple way by adding 0.5-5% by weight of a defrother, based on the total weight of the emulsion. Especially suitable are defrothers based on silicones or hydrocarbons, such as, for example, RD defrother emulsion from Dow Corning, Duesseldorf; the defrother "Nopco" by Munzing Chemie GmbH, Heilbronn; or the "Dehydran" types of Henkel KGaA.
Additionally, other auxiliary agents can be added to the emulsions, such as concrete thinners and accelerators (see European Laid-Open Application No. 0 090 434).
Concrete thinners based on melamine resins, such as, for example, "Melment" (manufacturer: Sueddeutsche Kalkstickstoff-Werke AG, D-8223 Trostberg) serve for increasing the fluidity of mortar mixtures. Their proportion is 0.1-8%, based on the total weight of the emulsion.
Accelerators effect a rapid and complete curing of the epoxy resin. Suitable accelerators are N- and P-containing compounds, conventional in principle, especially tertiary amines of up to 20 carbon atoms and esters of phosphorous acids of up to 25 carbon atoms, such as, for example, N-benzyldimethylamine and triphenylphosphite. They are used in amounts of 2-5%, based on the epoxide.
The emulsions are prepared by
first providing an aqueous solution of the emulsifier,
optionally adding a defrother,
adding the acid,
adding such an amount of diamine that a pH of 6-6.5 is attained,
optionally adding further auxiliary agents, such as, for example, concrete thinners and accelerators, and
finally stirring the liquid epoxy resin into the resultant mixture.
Deviations from this usual preparation method are possible and can be advantageous in certain cases. Thus, the sequence of adding the acid and the diamine can be reversed, for example. It is also possible to prepare the diammonium salt separately beforehand and then add same to the mixture. In all these cases, the decisive factor is that the pH value of the mixture must lie below 7, better below 6.5, at the time the epoxide is added under agitation. On the other hand, the pH value, should not be below 6, since otherwise the hydraulic binder is deprived of too much alkalinity. After the addition step is completed, the mixture is stirred for another 0.5-1.0 hour. In this way, emulsions are obtained which are stable for months at room temperature. In case of the occurrence of phase separation, the mixtures can be rapidly homogenized again by another agitation step.
The emulsions according to invention exhibit the property of being cured only in the presence of alkaline agents, such as inorganic bases, cement, and other alkaline-setting binders. Although curing is customarily conducted in the presence of cement, also suitable are curing mixtures which contain alkali hydroxides or alkaline earth hydroxides, calcium oxide, or other basic-reacting oxides. Mineral fillers, such as sand, finely ground silicon dioxide, and similar fillers, do not interfere with the curing process.
The emulsions according to the present invention are usable in an extremely variegated fashion in the construction field, wherein particular emphasis is given to application in the restoration of already existing buildings.
The emulsions of the invention are especially suited for use in the dry grouting method (method of dry application with a cement gun) (cf. DOS No. 31 36 737). For example, if it is desired to treat vertical walls, ceilings, pipes, or tunnels with concrete, concrete mixtures are required which adhere almost completely after being sprayed onto the wall surface. The present emulsions fulfill this requirement. By varying the amount of water, and other components, it is possible to prepare emulsions with differing synthetic resin/cement ratios meeting the requirements of the substrate. Preferably, the water/cement ratio is 0.35-0.65, and the ratio of epoxide and diamine to cement is 0.035-0.15.
Cured epoxy emulsion mortars have, as compared with conventional mortars, a higher resistance against water penetration, even when the water has chemicals, etc. dissolved therein. For this reason, the emulsions are excellently suited for the manufacture of prefabricated concrete parts, such as, for example, wastewater and sewage pipes.
Mastic and adhesive compositions based on hydraulically setting binders which are utilized, for example, in the tile art, advantageously contain the disclosed emulsions in amounts of between 3% and 75%. Adhesive strength and processing time correspond to the values required in this art.
The same also holds true for injection compositions based on hydraulically setting binders utilized for the restoration of buildings of all types. Here again, high adhesive strength is the determining factor.
Finally, the emulsions of the great invention are employed for the production of flooring plaster, especially if the surface is subjected to extraordinary loads.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
(a) Preparation of the Emulsions
(The quantitative data for oxalic acid refer in all cases to the dihydrate.)
EXAMPLE 1
A flat-bottomed flask with mechanical agitator is charged with 104 parts by weight of water, 44 parts by weight of an aqueous 10% polyvinyl alcohol solution ("PVAL" GH-20 of Nippon Synthetic Chemical Industry Co., Ltd.), and 4.5 parts by weight of a silicone-containing defrother (RD defrother of Dow Corning, Duesseldorf). In the resultant mixture, 30.3 parts by weight of oxalic acid is dissolved, and 40.6 parts by weight of isophoronediamine is added gradually drop by drop in portions so that a temperature of 80° C. is not exceeded. Thereupon, at a temperature of above 60° C., 173 parts by weight of the epoxy resin "Rutapox" VE 2913 is introduced. The mixture is allowed to cool down to room temperature, and then agitated for another hour. In this way, a stable, medium-viscosity emulsion is obtained which shows no changes whatever even after standing at room temperature for three months.
The diamines are abbreviated in the tables as follows:
______________________________________                                    
IPD =         isophoronediamine                                           
MPDA =        2-methylpentamethylenediamine                               
XDA =         xylylenediamine                                             
DDDM =        4,4-diamino-3,3'-dimethyldicyclo-                           
              hexylmethane                                                
TMD =         isomer mixture of 2,2,4- and 2,4,4-                         
              trimethylhexamethylenediamine                               
______________________________________                                    

                                  TABLE 1                                 
__________________________________________________________________________
           Examples                                                       
Composition                                                               
           1       2       3       4   5      6                           
__________________________________________________________________________
Water      104      47             260 200    470                         
Emulsifier.sup.4                                                          
            44     94.5    100     200 200    302                         
Defrother.sup.3                                                           
            4.5     5.0    1        10  10     29                         
Acid       Oxalic  Formic  Oxalic  Oxalic                                 
                                       Oxalic/                            
                                              Oxalic                      
           Acid    Acid    Acid    Acid                                   
                                       Formic Acid                        
                                       Acid                               
Acid Amount                                                               
           30.3    24.2    7        59 35/25.6                            
                                              207                         
Diamine    IPD     IPD     IPD     IPD IPD    IPD                         
Diamine Amount                                                            
           40.6    44.4    9.5     79.8                                   
                                        94    278                         
Concrete Thinner.sup.2                                                    
           --      --      --      --  --      30                         
Epoxy Resin                                                               
           "RUTAPOX"                                                      
                   "RUTAPOX"                                              
                           "RUTAPOX"                                      
                                   DER.sup.1                              
                                       "EPIKOTE"                          
                                              "RUTAPOX"                   
           VE 2913 VE 2913 VE 2913     828.sup.5                          
                                              VE 2913                     
Epoxy Resin Amount                                                        
           173     189     40      400 400    1,182                       
__________________________________________________________________________
 (Amounts given in parts by weight)                                       
 .sup.1 This is an epoxy resin mixture of "DER" 331 and "DER" 732         
 (manufacturer: Dow Chemical Rheinwerk, D7587 Rheinmuenster) in a weight  
 ratio of 7:3.                                                            
 .sup. 2 This is the concrete thinner "CERINOL" (14)BV liguid             
 (manufacturer: Deitermann, D4354 Datteln).                               
 .sup.3 This is the RD defrother emulsion (manufacturer: Dow Corning,     
 Duesseldorf).                                                            
 .sup.4 This is the polyvinyl alcohol "PVAL" GH20 (manufacturer: Nippon   
 Synthetic Chemical Industry Co., Ltd., Osaka, Japan), used in the form of
 a 10% aqueous solution.                                                  
 .sup.5 This is a product by Shell AG, Hamburg.                           

                                  TABLE 2                                 
__________________________________________________________________________
               Examples                                                   
Composition    7        8    9    10      11                              
__________________________________________________________________________
Water           99      65    50  130     100                             
Emulsifier     "COLLACRAL"                                                
                        "PVAL"                                            
                             "PVAL"                                       
                                  "POLYVIOL"                              
                                          "COLLACRAL"                     
               VL.sup.2 GH-20 .sup.1                                      
                             GH-20 .sup.1                                 
                                  V 03/20.sup.3                           
                                          VL.sup.2                        
Emulsifier Amount                                                         
               41.5     90   100  67      33                              
Defrother.sup.1                                                           
                3        5    5    5       5                              
Acid (and/or Ammonium Salt)                                               
               IPD/     Acetic                                            
                             IPD/ Formic  XDA/                            
               Oxalic   Acid Phthalic                                     
                                  Acid    Oxalic                          
               Acid          Acid         Acid                            
Amount         102      31.5  93  26      73                              
Diamine        --       IPD  --   MPDA    --                              
Diamine Amount --       42.3 --   32      --                              
Concrete Thinner.sup.1                                                    
               6.5      --   --   --      --                              
"CERINOL" 14-BV Liquid                                                    
Epoxy Resin.sup.4                                                         
               249      180  200  200     200                             
__________________________________________________________________________
 .sup.1 See corresponding footnote on Table 1.                            
 .sup.2 This emulsifier is a 30% aqueous solution of a copolymer based on 
 N--vinylpyrrolidone (manufacturer: BASF, Ludwigshafen).                  
 .sup.3 This is the 20% aqueous solution of a polyvinyl alcohol called    
 "POLYVIOL" V 03/20 (manufacturer: WackerChemie GmbH, Munich).            
 .sup.4 In all cases, this is the epoxy resin "RUTAPOX" VE 2913           
 (manufacturer: Bakelite, Duisburg).                                      

                                  TABLE 3                                 
__________________________________________________________________________
               Examples                                                   
Composition    12       13      14      15      16                        
__________________________________________________________________________
Water          150      50      40      100     20                        
Emulsifier     "COLLACRAL"                                                
                        "PVAL"  "PVAL"  "PVAL"  Poly-                     
               VL       GH-20.sup.1                                       
                                GH-20.sup.1                               
                                        GH-20.sup.1                       
                                                oxazoline.sup.2           
Emulsifier Amount                                                         
               30       100     100     120     70                        
Defrother.sup.1                                                           
                5        5      10       5       5                        
Acid (and/or Ammonium Salt)                                               
               Oxalic   Oxalic  Oxalic/ Tartaric/                         
                                                IPD/                      
               Acid     Acid    Formic  Oxalic  Oxalic                    
                                Acid    Acid    Acid                      
Amount         38       35      17.5/13 10/31   82                        
Diamine        DDDM     TMD     IPD     IPD     --                        
Diamine Amount 66       43.7    47       47     --                        
Epoxy Resin    "RUTAPOX"                                                  
                        "RUTAPOX"                                         
                                "RUTAPOX"                                 
                                        "RUTAPOX"                         
                                                "RUTAPOX"                 
               VE 2913  VE 2913 VE 2913 VE 2913 VE 2913                   
Epoxy Resin Amount                                                        
               200      200     200     200     200                       
__________________________________________________________________________
 .sup.1 See corresponding footnote on Table 1.                            
 .sup.2 This is the 20% aqueous solution of a polyoxazoline obtained      
 according to Example 6 of DOS 3,036,119 by polymerization of a mixture of
 70% 2isopropyl-Δ.sup.2oxazoline and 30%                            
 2methyl-Δ.sup.2oxazoline.                                          

              TABLE 4                                                     
______________________________________                                    
(Example 17)                                                              
                    Parts by                                              
Composition         Weight                                                
______________________________________                                    
Water               80                                                    
Emulsifier.sup.(1)  100                                                   
Defrother.sup.(1)   5                                                     
Formic Acid         10                                                    
Oxalic Acid         17.5                                                  
Dodecanedioic Acid  9                                                     
IPD                 47                                                    
Epoxy Resin "RUTAPOX"                                                     
                    200                                                   
VE 2913                                                                   
______________________________________                                    
 .sup.(1) See footnote on Table 1.
EXAMPLE 18
Analogously to Example 1, an emulsion was prepared without, however, an addition of defrother.
(b) Preparation of Epoxy Resin-Cement Mortars EXAMPLE 19
A mixture of 100 parts by weight of portland cement 35 F, 230 parts by weight of sand 0/1 mm, and 130 parts by weight of sand 1/2 mm was combined with 42.8 parts by weight of water and with 29.6 parts by weight of the emulsion of Example 1 and thoroughly intermixed. Analogously to DIN 1164, test specimens were produced, stored, and subjected to a strength test.
EXAMPLE 20
Analogously to Example 19, an epoxy resin-cement mortar was prepared from
100 parts by weight of portland cement 35 F
230 parts by weight of sand 0/1 mm
130 parts by weight of sand 1/2 mm
26.9 parts by weight of the emulsion of Example 2 and
45.3 parts by weight of water,
and tested in accordance with DIN 1164.
COMPARATIVE EXAMPLE A
A test specimen was produced in accordance with the standard DIN 1164 from
100 parts by weight of portland cement 35 F
230 parts by weight of sand 0/1 mm
130 parts by weight of sand 1/2 mm and
55 parts by weight of water,
and subjected to a strength test.
              TABLE 5                                                     
______________________________________                                    
Strength Test According to DIN 1164                                       
         Example A Example 19                                             
                             Example 20                                   
______________________________________                                    
Flexural                                                                  
tensile                                                                   
strength                                                                  
(N/mm.sup.2)                                                              
(a)        9.09        9.28      9.88                                     
(b)        6.14        9.21      9.08                                     
(c)        9.24        10.43     11.52                                    
Compressive                                                               
strength                                                                  
(N/mm.sup.2)                                                              
(a)        41.1        45.7      46.6                                     
(b)        29.3        39.3      35.2                                     
(c)        42.8        46.1      47.0                                     
______________________________________
The letters (a), (b), and (c) in Tables 5, 6, and 7 have the meanings below:
(a) 7 days of moist storage, then 21 days of inside storage,
(b) 28 days of inside storage,
(c) 7 days of moist storage, thereafter 35 days of inside storage.
EXAMPLE 21
Analogously to Example 19, an epoxy resin-cement mortar was produced from
100 parts by weight of portland cement 35 F
230 parts by weight of sand 0/1 mm
130 parts by weight of sand 1/2 mm
33.2 parts by weight of the emulsion of Example 3 and
28.0 parts by weight of water,
and tested in accordance with DIN 1164.
EXAMPLE 22
Analogously to Example 19, an epoxy resin-cement mortar was produced from
100 parts by weight of portland cement 35 F
230 parts by weight of sand 0/1 mm
130 parts by weight of sand 1/2 mm
19.4 parts by weight of the emulsion of Example 5 and
41.8 parts by weight of water,
and tested according to DIN 1164.
COMPARATIVE EXAMPLE B
Analogously to Comparative Example A, a cement mortar was prepared from
100 parts by weight of portland cement 35 F
230 parts by weight of sand 0/1 mm
130 parts by weight of sand 1/2 mm and
50 parts by weight of water,
and tested in accordance with DIN 1164.
              TABLE 6                                                     
______________________________________                                    
Strength Test According to DIN 1164                                       
         Example B Example 21                                             
                             Example 22                                   
______________________________________                                    
Flexural                                                                  
tensile                                                                   
strength                                                                  
(N/mm.sup.2)                                                              
(a)         8.7        11.5       9.5                                     
Compressive                                                               
strength                                                                  
(N/mm.sup.2)                                                              
(a)        52.5        56.0      50.5                                     
______________________________________
EXAMPLES 23.1-23.6
The following epoxy resin-cement mortar mixtures were prepared analogously to Example 19 and tested:
              TABLE 7                                                     
______________________________________                                    
(Data in Parts by Weight)                                                 
           Examples                                                       
Composition  23.1   23.2    23.3 23.4  23.5 23.6                          
______________________________________                                    
Portland cement                                                           
             100    100     100  100   100  100                           
35 F                                                                      
Sand 0/1 mm  200    200     200  200   200  200                           
Sand 1/2 mm  100    100     100  100   100  100                           
Water        42.5    58     38.4 53.9  37.1 52.6                          
Emulsion of Ex. 14                                                        
             --     --      12.5 12.5  16.6 16.6                          
Flexural tensile                                                          
strength (N/mm.sup.2)                                                     
(a)          9.4     6.3    11.7 11.1  11.8 10.4                          
Compressive                                                               
strength (N/mm.sup.2)                                                     
(a)          59.5   38.7    56.6 44.8  57.0 46.7                          
______________________________________
(c) Production of Adhesive Compositions EXAMPLE 24
An adhesive composition was prepared from 100 parts by weight of portland cement 35 F and 58 parts by weight of the emulsion according to Example 18 and was cured into test specimens. After 3 days of storage under moist conditions and 4 days of inside storage, the following strength data were determined:
Flexural tensile strength: 11.5 N/mm2
Compressive strength: 71.6 N/mm2
Tensile adhesion to steel: 1.6 N/mm2
Tensile adhesion to concrete: 3.1 N/mm2
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims (24)

What is claimed is:
1. A stable epoxy resin-diammonium salt emulsion comprising
(a) a liquid epoxy resin,
(b) water,
(c) an emulsifying means comprising at least one of
I. a polyvinyl alcohol obtained by saponification of polyvinyl acetate with a degree of hydrolysis of at least 70% and a molecular weight of at least 5,000,
II. a polyoxazoline having a molecular weight of 10,000-100,000, or
III. a copolymer of N-vinylpyrrolidone with
vinyl esters of mono- or dibasic carboxylic acids of up to 6 carbon atoms,
(meth)acrylic esters of mono- and dihydric alcohols of up to 6 carbon atoms,
maleic, fumaric, crotonic acid or
styrene, and
(d) a latent curing agent comprising a salt of
I. a diamine of the formula H2 N--CH2 --R--NH2, or H2 N--R--CH2 --R--NH2 wherein R is a member selected from the group consisting essentially of
an unsubstituted C4-9 -alkylene residue, or a C4-9 -alkylene residue substituted by oxygen,
an unsubstituted C6-9 -cyclo-alkylene residue, or a C6-9 -cyclo-alkylene residue substituted by oxygen, and
a C7-9 -arylkylene residue, with
II. an aliphatic, cycloaliphatic, or aromatic mono- or dicarboxylic acids of up to 12 carbon atoms, said latent curing agent exhibiting curing properties only in the presence of an alkaline agent.
2. An epoxy resin-diammonium salt emulsion according to claim 1, wherein the polyvinyl alcohol component of the emulsifier has a molecular weight of 10,000-100,000.
3. An epoxy resin-diammonium salt emulsion according to claim 2, wherein the polyvinyl alcohol is present in a quantity of 0.5-40%.
4. An epoxy resin-diammonium salt emulsion according to claim 1, wherein the dicarboxylic acid component of the latent curing agent is phthalic acid, tartaric acid, adipic acid, oxalic acid, acetic acid or formic acid or their mixture.
5. An epoxy resin-diammonium salt emulsion according to claim 1, wherein the diamine component of the latent curing agent is a cyclic diamine of 8 or 9 carbon atoms.
6. An epoxy resin-diammonium salt emulsion according to claim 5, wherein the diamine component is isophoronediamine.
7. An epoxy resin-diammonium salt emulsion according to claim 1, wherein the diamine component of the latent curing agent is an aliphatic diamine of 6-9 carbon atoms substituted by 1-3 methyl groups.
8. An epoxy resin-diammonium salt emulsion according to claim 7, wherein the aliphatic diamine is 2,2,4- or 2,4,4-trimethylhexamethylenediamine.
9. An epoxy resin-diammonium salt emulsion according to claim 7, wherein the aliphatic diamine is 2-methylpentamethylenediamine.
10. An epoxy resin-diammonium salt emulsion according to claim 1, which contains a silicone or hydrocarbon defrother.
11. An epoxy resin-diammonium salt emulsion according to claim 1, which contains thinners, accelerators or other conventional auxiliary agents for concrete.
12. An epoxy resin-diammonium salt emulsion according to claim 1, wherein the amount of water is 30-250%, based on the amount of epoxy resin.
13. An emulsion according to claim 1, wherein the aliphatic, cycloaliphatic, or aromatic mono- or dicarboxylic acid of (d) II is hydroxy-substituted.
14. A process for the production of the epoxy resin-diammonium salt emulsion according to claim 1 comprising:
(a) providing an aqueous solution of the emulsifier,
(b) adding the mono- or dicarboxylic acid to the solution
(c) adding the diamine to bring the pH of the solution to between 6.0 and 6.5, and
(d) stirring the liquid epoxy resin into the solution.
15. A process according to claim 14, wherein a defrother is added prior to adding the dicarboxylic acid.
16. A process according to claim 14, wherein an auxiliary agent is added after bringing the pH of the solution to 6.0-6.5.
17. A process for the production of the epoxy resin-diammonium salt emulsion according to claim 1, comprising:
(a) providing an aqueous solution of the emulsifier,
(b) adding the diamine to the solution,
(c) adding the mono- or dicarboxylic acid to bring the pH of the solution to between 6.0 and 6.5, and
(d) stirring the liquid epoxy resin into the solution.
18. In an epoxy resin-cement mortar, the improvement wherein the mortar contains the epoxy resin-diammonium salt emulsions of claim 1.
19. In a method of curing a cement mixture comprising an alkaline-reacting compound, the improvement wherein the curing agent contains the epoxy resin-diammonium salt emulsion of claim 1.
20. A method of curing an epoxy resin emulsion of claim 1, comprising admixing therewith an effective amount of an alkaline agent.
21. A method of claim 20, wherein the alkaline agent is cement.
22. In a method of dry grouting, the improvement wherein the grout contains epoxy resin-diammonium salt emulsion of claim 1.
23. In mastic compounds based on hydraulically setting alkaline binders, the improvement wherein the binder contains an epoxy resin-diammonium salt emulsion of claim 1.
24. In adhesive compounds based on a hydraulically setting alkaline binder, the improvement wherein the binder contains an epoxy resin-diammonium salt emulsion of claim 1.
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US4967839A (en) * 1989-10-23 1990-11-06 Atlantic Richfield Company Method and composition for cementing in a wellbore
US5609680A (en) * 1992-12-21 1997-03-11 Maeta Concrete Industry Ltd. Cement, cement products, molding material, a concrete member and a method of producing the same
US20050248441A1 (en) * 2001-10-02 2005-11-10 Telkonet Communications, Inc. Method and apparatus for attaching power line communications to customer premises
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US5567748A (en) * 1991-12-17 1996-10-22 The Dow Chemical Company Water compatible amine terminated resin useful for curing epoxy resins

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US4967839A (en) * 1989-10-23 1990-11-06 Atlantic Richfield Company Method and composition for cementing in a wellbore
US5609680A (en) * 1992-12-21 1997-03-11 Maeta Concrete Industry Ltd. Cement, cement products, molding material, a concrete member and a method of producing the same
US5614009A (en) * 1992-12-21 1997-03-25 Maeta Concrete Industry Ltd. Cement, cement products, molding material, a concrete member and a method of producing the same
US5651816A (en) * 1992-12-21 1997-07-29 Maeta Concrete Industry Ltd. Cement, cement products, molding material, concrete member and a method of producing the same
US20050248441A1 (en) * 2001-10-02 2005-11-10 Telkonet Communications, Inc. Method and apparatus for attaching power line communications to customer premises
US20110123453A1 (en) * 2008-07-10 2011-05-26 Serina Therapeutics, Inc. Polyoxazolines with Inert Terminating Groups, Polyoxazolines Prepared from Protected Initiating Groups and Related Compounds
US8883211B2 (en) 2008-07-10 2014-11-11 Serina Therapeutics, Inc. Polyoxazolines with inert terminating groups, polyoxazolines prepared from protected initiating groups and related compounds
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